Method of refining hydrocarbon oils



june 2, 1936. A. LACHMAN METHOD OF REFININQ HYDROCARBON OILS OriginalFiled June 27, 1930 Q in Tim!

lNVENTOR HE THUE L/VC HNi/V BY Patented June 2, I936 UH I STATES ATENTOFFICE 2,042,718 METHOD OF REFINING HYDROCARBON OILS Arthur Lachman,Berkeley, Calif.,

mesne assignments, t esses Inc., a corporati assignor, by

0 Vapor Treating Procon of California Application June 27, 1930, SerialNo. 464,350

Renewed Fe cracking or tion is a continuation in part of my pendingapgasoline stock is With a Water solutlon of an alkali with water. Thistreatment removes most of the bruary 6,

corrosive sulphur compounds into non-corrosive bodies.

gasoline after the purifipounds into compounds that may be extracted toa high extent with the metal salt solution employed. Also which mayassist in the polymerization of the unstable, unsaturated hydrocarbonsand thereby produce a gasoline stock which is low in sulphur content,sweet to the doctor test and contains substantially no gums or gumforming constituents.

The hydrocarbon oil stock to be treated by my invention may or may nothave had a preliminary treatment with sulphuric acid or other agents topartly purify the same, or may be first partly purified by my inventionand the purification completed by methods known 1 art, such as treatmentwith caustic alkali, sulphuric acid, In case of gasoline stocks producedby cracking high sulphur bearing crude petroleum oil or residuum, it maybe advantageous to treat such gasoline stocks with small amounts ofsultreatment with a water any of the aiorestated metal salts or mixturesthereof, which may also be followed by treatment with an alkali watersolution of sodium, potassium, or calcium hydroxide, carbonates ofsodium or potassium.

Although a solution of less concentration may be employed which mayrange from 50 or less to approximately 85 per cent, the strength of thewater solution of the metallic salt or mixtures of salts employed ispreferably a substantially concentrated solution and the temperatureemployed for the treatment is approximately 300 to 400 degrees F., whichnormally fluctuates, depending upon the vaporizing temperature of theoil under treatment.

One of the principal objects of this invention is to accomplish adesulphurization and purification of gasoline stock by a vapor phasetreatment with a water solution of a metallic salt or salts at thereacting temperature in the presence of air.

Another object of the invention is to provide a. rapid and economicalprocess for purifying gasoline stock produced by the thermo moleculardecomposition of higher boiling petroleum oils by treating the same withan agent capable of polymerizing all of the unstable hydrocarbonscontained therein and at the same time remove all the corrosive sulphurcompounds and render the gasoline sweet to the doctor test.

Another object of the invention is to provide an economical method forimproving the color, removing sulphur compounds, gums and gum formingmaterial from gasoline or naphtha stocks, so that the same may be keptin storage for relatively long periods of time without change in qualityby the formation of polymerized bodies.

Other objects and advantages will be apparent from the preferredembodiment of this invention which will now be more fully explained byreference to the accompanying drawing, which is a diagrammaticalrepresentation of an apparatus in which the invention may be carriedout.

Referring to the drawing, it indicates a pipe leading to a source ofcrude gasoline vapors coming from a vaporizing chamber or fractionatingtower not shown. Pipe iii is connected to jet mixer 14, the flow ofcrude gasoline vapors being controlled by operating valve ll. Pipe 15controlled by valve !8 leads to an air supply not shown. The quantity ofair introduced into the jet mixer l4 ranges from approximately 4 cubicfeet to as much as 12 cubic feet or more, per barrel of liquid gasolinesupplied calculated at 60 degrees F. and 760 mm. pressure, the quantityof air employed depending upon the extent of oxidation required toobtain a sweet gasoline substantially free from sulphur, gums and gumforming constituents. The air supply may also be measured as apercentage of the volume of vapors 5 being treated. The volume of addedair normally varies from 0.5 to 1.5 per cent, measured at the sametemperature and pressure as the vapors. Pipe 2 connects the jet mixer Mto treating towe B at the point 9 below the contact 10 material 3. Pipe8 controlled by valve 2| leads to a supply of water or steam not shown.Pipe !3 controlled by the valve 2% is connected to pipe 8 and leads to asource of air supply not shown, by means of which air may be introducedinto treating tower B along with water or steam instead of through thepipe i5. 13 indicates in general a tower of suitable height and diameterfilled with resistant or contact material such as fire brick, spiraltile, rock or the like, indicated by the numeral 3, which forms tortuouspassages through the tower, although it is to be understood that thewell-known bubble cap contact tower may be employed. Disposed above thetower or adjacent to the same, is a tank I2 containing a water solutionof a metallic salt or mixtures of the same, as heretofore enumerated,having a concentration of from 59 per cent or less to as high asapproximately 85%. Preferably a substantially concentrated watersolution of zinc chloride containing an oxide or hydroxide is employed,although a solution of less concentration may be used, the concentrationdepending upon the stock under treatment and the product desired. Tanki2 is connected to tower B by .means of a pipe 4, having a regulatingvalve 5. The pipe d terminates over a spreader plate 6 and this plateevenly distributes the water solution of the metallic salt or salts,when the valve 5 is open, over the brick work or contact material. Thewater solution of the metallic salt or salts flows downward through thiscontact material and may finally be discharged through the bottom by apipe 1, controlled by valve l9, to a storage not shown and may bethereafter recovered for reuse. As heretofore stated, tower B isprovided with a steam or water inlet pipe 8, which may intermittently orcontinuously supply a predetermined amount of water or steam to thetower B. The hot gasoline vapors coming through the pipe it enters themixer M wherein they are continuously mixed with the required amount ofair coming through the pipe l5 regulated by valve I8. The quantity ofair introduced may range from approximately 4 to 12 cubic feet or moreper barrel of gasoline stock to be treated. From the mixer Hi thegasoline vapors commingled with the required amount of air passesthrough pipe 2 and enters the lower section of the tower B at a point 9.The gasoline vapors commingled with the introduced air pass up throughthe numerous tortuous passages in the brick-work and thereby come intointimate contact with the said water solution of metallic salt or saltsflowing over the contact material 3. Although other temperatures may beemployed, the water solution of metallic salt or salts, gasoline vaporsand air are generally maintained at a temperature of approximately 300to 400 degrees F. The purified gasoline vapors and air after passingthrough the tower B are discharged at the upper end of the tower Bthrough a pipe it! which is connected with a condenser H of suitableconstruction. From condenser H the condensed purified gaso- 2,042,718 3lin and i m products pas hr u h pip of water when a larger amount of asolution of certain amount of water from the water soluthe aeriformproducts, are sweet to the doction of the metallic salt or salts and thepurpose tor test and suitable for use as refined gasoof the steam orwater inlet 8 is that of mainline stock of high purity with a lowsulphur containing the solution at approximately a certain tent.

water content so as to maintain the necessary While the process hereindescribed is well said solution is admitted for each barrel of gaso- 11moil from the aeriform productsline stock under treatment and acorresponding A process of refining mineral 011$, Comprisamount of thespent solution is withdrawn at vaporizing mineral 011 by the applicationthe same time. The amount of water vapor reof heat, Commingling the apzed mineral oil quired to replace the vaporized Water from the W th aand Contacting the heated vaporized water solution of metallic salt orsalts varies mineral O nd the a W a ma ntained subwithin wide limits,depending upon th on stantially concentrated Water solution of zinctration of the solution employed, the temperasalt other than zinciod1de, separating, condensture at which the operation is carried out,the ing and collecting a purified mineral oil from nature and amount ofthe inert gases which products of reaction, treating solution andaeritreated and the air employed for the oxidizing 47 A process ofrefining mineral oils, comprisreaction. Approximately 50 to 100 poundsof ing, commingling vaporized mineral oil with air,

rified mineral oil from products of reaction, treating solution andaeriform products.

5. A process of refining mineral oils, comprising, vaporizing a mineraloil by the application of heat, contacting the heated vaporized mineraloil with a maintained heated water solution of a zinc salt other thanzinc iodide and air and then separating, condensing and collecting apurified mineral oil from products of reaction, treating solution andaeriform products.

6. A Process of refining mineral oils, comprising, vaporizing a mineraloil by the application of heat, commingling the vaporized oil with amaintained water solution of a zinc salt other than zinc iodide in thepresence of air, heated to a temperature of not less than the vaporizingtemperature of the vaporized mineral oil under treatment, and thenseparating, condensing, and collecting a purified mineral oil fromproducts oi reaction, treating solution and aeriform products.

'7. A process of refining mineral oils, comprising, heating a mineraloil to form a vapor at a temperature of approximately 300 to 400 degreesF., contacting the heated vapor with a maintained'water solution of zincsalts other than zinc iodide and air maintained at a substantiallysimilar temperature, then condensing and collecting a purified mineraloil, separated from products of reaction, treating solution and aeriformproducts.

8. A process of refining mineral oils, comprising, commingling a mineraloil vapor at temperatures of approximately 300 to 400 degrees F., withair and a maintained water solution of zinc salt other than zinc iodidemaintained at a substantially similar temperature, the water solution ofzinc salt having a concentration of approximately 50-85 then condensingand collecting a purified mineral oil, separated from products ofreaction, treating solution, and aeriform fluids.

9. A process of refining mineral oils, comprising, heating, a mineraloil to form a vapor, contacting the heated vapor commingled with air,with a maintained water solution of zinc salt other than zinc iodidecontaining zinc hydroxide and then separating, condensing and collectinga purified mineral oil from products of reaction, treating solution andaeriform fluids.

10. A process of refining mineral oils, comprising, heating a mineraloil to form a vapor, passing the heated vapor commingled with airthrough and in contact with a maintained water solution of zinc saltsother than zinc iodide containing iromJ/ of 1 per cent to 3 per cent byweight of zinc hydroxide and then separating, condensing and collectinga purified mineral oil, from products of reaction, treating solution andaeriform fiuids.

11. A process of refining mineral oils, comprising, heating a mineraloil to form a vapor, passing the heated vapor commingled with airthrough and in contact with a maintained water solution of zinc saltother than zinc iodide containing from of 1 per cent to 3 per cent byWeight zinc hydroxide and zinc oxide and then separating, condensing andcollecting a purified mineral oil from products of reaction, treatingsolution and aeriform fiuids.

12. A process of refining mineral oils, comprising, heating a mineraloil to form a vapor, passing the heated vapor commingled with heated airthrough and in contact with a water solution of zinc salts other thanzinc iodide, maintaining the solution in a fiuid condition by theadditions of water, condensing and collecting a purified vapor of themineral oil after passing through the solution.

13. A process of refining mineral oils, comprising, commingling thevapors of a mineral oil containing air with a maintained water solutionof 5 zinc salt other than zinc iodide and then condensing and separatingtreated mineral oil vapors from aeriform products.

14. A process of refining mineral oils, comprising, heating a mineraloil to form a vapor, passing 10 the heated vapor containing air throughand in contact with a water solution of zinc salt other than zinc iodidecontaining zinc hydroxide, maintaining the solution in a fluid conditionby the addition of water during contact of the vapors and 15 air withthe treating solution and condensing the vapor after passing through thesolution.

15. A process of refining mineral oils, comprising, heating a mineraloil to form a vapor, passing the heated vapor commingled with airthrough 20 and in contact with a water solution of zinc salts other thanzinc iodide containing from of 1 per cent to 3 per cent by weight ofzinc hydroxide and zinc oxide, maintaining the solution in a fluidcondition by addition of Water during contact of 25 the vapors and airwith the treating solution and condensing the vapor after passingthrough the solution.

16. A process of refining mineral oils, comprising, heating a mineraloil to form a vapor, pass- 30 ing the heated vapor commingled with airthrough and in contact with a. water solution of zinc salts other thanzinc iodide, maintaining the concentration of the solution withinpredetermined limits by the addition of water, condensing and col- 35lecting the refined mineral oil vapors after passing through thesolution.

17. A process of refining mineral oils, comprising, heating a mineraloil to form a vapor at a temperature of approximately 300 to 400 degreesF., passing the heated vapor commingled with air through and in contactwith a water solution of zinc salts other than zinc iodide maintained ata similar temperature and having a concentration of approximately59-85%, 45 maintaining the concentration of the solution as specified,by the continuous addition of water and then condensing the refinedmineral oil vapors after passing through the solution.

18. A process of refining mineral oils, comprising, vaporizing a mineraloil, contacting the vaporized mineral oil commingled with air with awater solution of zinc salt other than zinc iodide, intermittentlyintroducing water into the solution of zinc salt to maintain the salt insolution and continuously condensing and collecting purified mineral oilvapors separated from the products of reaction, aeriiorm fiuids andsolution of zinc salt.

19. A process of refining mineral oils, comprising, heating a mineraloil to form a vapor, passing the vapor commingled with air through andin contact with a water solution of zinc salts other than zinc iodidecontaining zinc hydroxide, intermittently introducing Water into thesolution of zinc salts containing zinc hydroxide to maintain the saltsin solution and continuously condensing and collecting purified mineraloil vapors separated from the products of reac- 70 tion, solution ofzinc salts and 'aeriform fiuids.

20. A process of refining mineral oils, comprising heating a mineral oilto form a vapor, passing the vapor commingled with air through and incontact with a water solution of zinc salt 75 other than zinc iodidecontaining zinc oxide, inand then condensing and separating themintermittently introducing Water into the solution era] oil fromaeriform products. OI zinc salt containing zinc oxide to maintain 2. Aprocess of refining mineral oils comthe treating solution, products ofthe reaction tacting the commingled vapors and air with a and aeriformproducts. maintained water solution of heavy metal salt

